Permanently having and permanently setting of hair

ABSTRACT

Process for permanently waving hair and permanently setting hair which inclides the steps of subjecting hair on rollers and applying a self neutralizing composition containing in mixture a thiol selected from the group consisting of: thioglycerol, thioglycolic acid, dimercapto-adipic acid, dimercapto-1,4 butanediol-2,3 and thiolactic acid, and a disulfide, aid disulfide being dithiodiglycerol, or dithiodiglycolic acid only when the thiol is thioglycolic acid, and wherein the amount of thiol is preferably about 2 - 5 percent weight of the composition and wherein the numerical ratio of the disulfide groups to thiol groups is greater than 1,5, or greater than 2 when the thiol is thioglycolic acid and the disulfide is dithiodiglycolic acid.

United States Patent [1 1 Kalopissis et al.

[ 1 Oct. 30, 1973 PERMANENTLY WAVING AND PERMANENTLY SETTING OF HAIR[75] Inventors: Gregoire Kalopissis; Paul Roussopoulos, both of Paris;Charles Zviak, Franconville, all of France [73] Assigneei SocieteAnonyme dite: L'Oreal, Paris, France [22] Filed: Jan. 31, 1972 [21]Appl. No.: 222,299

Related US. Application Data [63] Continuation-impart of Ser. No.56,136, July 6, 1970, which is a continuation of Ser. No. 475,890, July29, 1965, and a continuation-in-part of Ser. No. 14,757, Feb. 25, 1970,which is a continuation of Ser. No. 508,383, Nov. 17, 1965.

[52] US. Cl. 132/7, 424/72 [51] Int. Cl. A45d 7/00 [58] Field of Search132/7; 424/72, 71

[56] References Cited UNITED STATES PATENTS 10/1955 Sanders 424/7210/1955 Haefele 424/71 2,689,815 9/1954 Gershon 424/72 FOREIGN PATENTSOR APPLICATIONS 810,355 3/1959 Great Britain l67/87.l

1,336,311 7/1963 France l67/87.l

Primary Examiner-Louis G. Mancene Assistant Examiner-Gregory E. McNeil]Attorney-Mason, Mason & Albright 57 ABSTRACT composition and wherein thenumerical ratio of the disulfide groups to thiol groups is greater than1,5, or greater than 2 when the thiol is thioglycolic acid and thedisulfide is dithiodiglycolic acid.

8 Claims, No Drawings PERMANENTLY WAVING AND PERMANENTLY SETTING OF HAIRCROSS REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of Ser. No. 56,136 filed July 6, 1970, and Ser. No.14,757 filed Feb. 25, 1970, which are continuations of applications Ser.Nos. 475,890 and 508,383 respectively filed July 29, 1965, and Nov. 17,1965.

BACKGROUND OF THE INVENTION It is common knowledge that hair waving canbe done in three ways, namely:

the process of permanent deformation of the hair;

the process of simple setting; and

the process of permanent setting.

A. Permanent Deformation of the Hair (Permanent waving) The permanentdeformation of the hair conventionally includes the following steps:

1. Rolling the hair on permanent-wave rollers of relatively smalldiameter, for example 8 to 10 mm.

2. Saturating the hair with a so-called reduction agent, such as athiol. It should be noted, however, that the saturation of the hair withthe reduction agent can be done before rolling the hair on thepermanent-wave rollers.

3. Rinsing the hair, still on rollers (Optional).

4. Saturating the hair, still on permanent-wave rollers, with aneutralizing or oxidizing agent, such as a solution of hydrogenperoxide.

5. Removing the permanent-wave rollers and rinsing the hair.

By this process of permanent deformation of the hair, stable and durablecurls are produced called pennanent which are not affected byatmospheric humidity or even by shampooing.

B. Simple Setting.

The conventional process of simple setting includes the following steps:

1. Saturating the hair with a hair setting lotion which can be eithernatural water, or a water-based solution, or a resin-basedhydroalcoholic solution.

2. Rolling the hair on rollers of to 30 mm. in diameter.

3. Drying the hair, still on rollers.

By this process a temporary wave is obtained which may last for a fewdays, but which is not designated by the term permanent wave," becauseshampooing washesaway the wave.

C. Permanent Setting.

The conventional process of permanent setting is, in fact, a compromisebetween the permanent deformation process and the simple settingprocess.

.The conventional process of permanent setting includes the followingsteps:

1. Rolling the hair on rollers of about 15 to mm. in diameter. I

2. Saturating the hair with a reducing" agent. As in the process ofpermanent deformation, the hair can be saturated before it is rolled onthe rollers.

3. Rinsing (Optional).

4. Saturating the hair, still on rollers, with a neutralizing oroxidizing agent.

5. Rinsing the hair, still on rollers.

6. Drying the hair, still on rollers, after it has been eventuallysaturated with a setting solution, either a water-based solution or aresin-based hydroalcoholic solution.

By this process a permanent setting is obtained which, compared toprocess B, has the advantage of giving the hair a relatively stable wavewhich shampooing will not wash out, but which is less durable than thewave obtained in permanent waving.

The process of permanent setting makes use of compounds similar to thoseemployed for permanent deformation of the hair, but generally lessconcentrated; moreover, the diameter of the rollers used is greater thanthat of the rollers used in permanent waving; and, finally, as in theprocess for simply setting, the hair, still on rollers, is allowed todry.

As can be readily observed, the process of permanent deformation of thehair, as well as the process of permanent setting, comprises a number ofsteps which present numerous inconveniences.

Indeed, the fact that two different solutions must be applied one afterthe other, each having been left to stand from 15 to 20 minutes,notwithstanding the necessity of separate rinsings, constitutesoperational complications.

Moreover, the step called neutralization or oxidation is a particularlydifficult one, because the oxidizing agent penetrates the hair only withdifficulty. Care must be taken not to use too much of this liquid whichis slightly corrosive, lest it touch the scalp and damage the personsskin.

It must be noted, however, that certain attempts have been made toaccomplish the so-called neutralization or oxidation step by restoringto the mere oxidizing action of the oxygen in the air.

By resorting to this modified process, however, a period of 5 to 8 hoursis necessary if satisfactory results are to be obtained. The hair,constrained in the style that one wishes to obtain, needs that longexposure to the oxygen of the air in order to obtain the desired effect.

In order to simplify these operations, the applicants have sought todevelop a process whereby the application of one and only one solutionwould produce simultaneously the results of the step called reductionand that called neutralization or oxidation.

A priori, such a simplification would appear difficult to realize; theprocess of permanent reduction of the hair is based on the opening ofthe cystine bridges by means of a reducer followed by the reconstitutingof the same by means of an oxidizing agent. In order to producedeformation in a single step, it is therefore necessary to mix twosubstances -'one a reducer, the other an oxidizer which tend naturallyto react on each other and which, at first, would seem to cancel outeach others action on the hair.

The applicants realized, however, that during the first step it wasnotnecessary to open all the SS--- bridges before proceeding to closethem, after having provoked the relative displacement of the keratinicchains. It would suffice to provoke a continual opening and closing of acertain number of keratinic bridges, during which time the hair would bekept in a sufficient state of deformation to provoke the slipping of thekeratinic chains along with the opening of their -S-S- bridges.

The present invention is therefore as relevant to a new process ofpermanent deformation of the hair as it is to a process of permanentsetting, both of these processes being effected in a single step.

According to the invention, in order to effect these two processes, onewould utilize one and only one composition containing a mixture ofcertain thiols and certain disulfides in well determined proportions, sothat a genuine self-neutralizing composition is obtained which makespossible in one operation the permanent deformation as well as thepermanent setting of the hair, a process which until now required twosteps, namely, the so-called reduction step and the so-calledneutralization or oxidation step.

Compositions based on thiols and disulfides of various kinds havealready been described in US. Pat. Nos. 2,719,813 and 2,719,814.

It should be noted, however, that in both of these patents, the use ofsuch compositions is recommended in the first step only of the permanentdeformation of hair, the presence of the disulfide being justified bythe fact that the latter compounded with the thiol diminishes the harsheffects of the thiol.'

In fact, it is known that thiols have certain secondary effects causingdamage to hair keratin.

To offset the harmful action of the thiols, it is recommended in theAmerican patents to use thiol along with a disulfide in a numericalratio of the disulfide groups to thethiol groups contained between 0.1to 1.5. In these numerical ratios, the disulfides mitigate the harsheffects of the thiols without removing the reducing power of the latter.

According to these patents, it is specified, moreover, that a numericalratio of the disulfide groups to the thiol groups in excess of 1.5precludes curls of superior quality, whatever the duration of theapplication.

Consequently, for the first step in permanent waving it is recommendedto contain the numerical ratios of the disulfide groups to the thiolgroups between 0.25 and 0.75.

Finally, it is importantto specify that, according to the two patents,the second step called neutralization or oxidation is effected either bymeans of an oxidizing compound or by simple exposure of the hair to theoxygen to the atmospheric air.

These two patents contribute progress to the conventional process ofpermanent deformation, since they permit elimination of the harshness ofthe thiols, but they give'neither solution nor insights into the problemcaused by the permanent deformation of the hair in one step by means ofa self-neutralizing composition.

SUMMARY OF THE INVENTION As has been explained above, the presentinvention offers a solution to the problem causing the steps ofpermanent deformation and permanent setting of the hair, because itallows completion of these two processes in only one step.

The object of the present invention is to provide a new process toeffectthe permanent deformation of the hair in a single step, said processbeing characterized by the following:

the hair subjected to a sufficient mechanical deformation is treated bymeans of a composition containing in mixture from 2 to 5 percent of athiol taken in the group constituted by thioglycerol, thioglycolic acid,dimercapto-adipic acid, dimercapto-1,4 butanediol-2,3

and thiolactic acid, and a disulfide which is dithiodiglycerol. Thenumerical ratio of the disulfide groups to the thiol groups is greaterthan 1,5 and the said composition has a pH between 8,5 and 10.;

the composition mentioned above is permitted to take effect during aperiod of time from 5 to 30 minutes;

the hair is rinsed; and

the means affording the mechanical deformation is then removed.

According to a variation of the present invention, the permanentdeformation of the hair can also be accomplished in one step, asindicated above, by using a selfneutralizing composition, a compositioncontaining a mixture of 2 to 5 percent of thioglycolic acid for thioland dithiodiglycolic acid for disulfide, the numerical ratio of thedisulfide groups to the thiol groups being greater than 2, and thecomposition having a pH contained between 8.5 and 10.

The numerical ratios of the disulfide groups to the thiol groups whichin the first case must be greater than 1.5 and in the second greaterthan 2, are critical ratios, that is to say, below these limits nodeformation is obtained, or only a deformation of inferior quality whichin no case can be considered permanent according to the criteriagenerally accepted. Among these criteria the index of fixation, If, isparticularly selective, and it is generally accepted that permanentwaving is produced when this index is equal to or less than 0.1. ByIndex of Fixation is meant the following ratio:

extension The calculation of the Index of Fixation consists therefore inmeasuring the force T corresponding to the area of plasticity of thehair, hence the minimum force allowing the hair to be subjected to adeformation greater than 2 percent. This force is measured:

before the treatment, and this gives the value T,;

after the treatment, with the help of a selfneutralizing composition,and this gives the value T and finally;

after the total fixation, that is to say, after the reconstruction ofthe ensemble of bridges -SS- of the hair keratin, by means of thehydrogen peroxide, and this gives the value T The thiol concentrate isnot exactly critical, but it has been established that such aconcentrate from 2 to 5 percent brings about compositions possessing therequired fluidity. In fact, some concentrates stronger in thiol wouldproduce strong disulfide concentrates ally recommended for capillarycompositions so that there is no incompatibility between the scalp andthe composition.

According to the invention, in the process of permanent deformation ofthe hair, deformation results either in waves or in straightening. Toobtain a permanent wave, the mechanical device used is the permanentwave roller having a diameter of about 8 to 10 mm.

On the other hand, to obtain straightening, mechanical deformation isobtained by combing and by the application of a composition having acream-like consistency, and this makes it possible to keep the hair inthe desired configuration.

According to the invention, and as in the classical procedure forpermanent deformation of the hair, the self-neutralizing compositionssuch as they are defined above, must be applied either before or afterusing the mechanical device which brings about the mechanicaldeformation. After the waiting time of 5 to 30 minutes, as indicatedabove, the mechanical device is removed and the hair is rinsed.

By this process, according to the invention of permanent deformation ofthe hair, curls of excellent quality are obtained which resistatmospheric humidity and subsequent shampoos.

PREFERRED EMBODIMENTS The object of the present invention also includesa process of permanent setting characterized by the fact that:

the hair, subjected to a slight mechanical deformation by means of tomm. rollers, is treated with a composition containing a mixture of 2 to5 percent thiol taken from the group consisting of thioglycerol,thioglycolic acid, dimercaptoadipic acid, dimercapto- 1,4 butanediol 2,3and thiolactic acid, and a disulfide, the disulfide beingdithiodiglycerol. The numerical ratio of the disulfide groups to thethiol groups is greater than 1.5 and the aforesaid composition has a pHbetween 8,5 and 10.;

the aforementioned composition isleft to react during a 5 to 30 minuteperiod of time;

the hair is eventually rinsed; and

the hair, still on rollers, is dried by heat externally provided.

As in the process of permanent deformation of the hair, it is alsopossible, according to the invention, to utilize a compositioncontaining a mixture of 2 to 5 percent thioglycolic acid (for thiol) andof dithiodiglycolic acid (for disulfide), the'numerical ratio of thedisulfide groups to the thiol groups being greater than 2 and thecomposition having a pH between 8,5 and 10.

According to this permanent setting process, beautiful waves areproduced, identical to those obtained by the classical process involvingtwo steps.

As can be ascertained, the self-neutralizing compositions used in theprocess producing permanent deformation of the hair and the process ofpermanent setting are of the same kind and therefore are judged by thesame criteria.

In a variation of the permanent setting process, it is possible, afterrinsing the hair, to apply to it a waterbased or a resin-basedhydroalcoholic setting lotion.

Compositions producing simultaneously permanent deformation andpermanent setting of the hair can appear in various forms. It ispreferable, however, to utilize water-based or hydroalcoholic solutions(ethanol water, for example) which can contain other ingredients, suchas perfumes, swelling agents, etc. To obtain straightening of the hair,it is preferable to use creamytextured compositions which allow the hairto be held in the desired configuration.

Finally, it should be noted that when, in the processes of theinvention, compositions are used that are formed by pairing thefollowing thiol/disulfide: thioglycerol/dithiodiglycerol, andthioglycolic acid/dithiodiglycolic acid, the required quantity ofdisulfide can be obtained at the precise moment of application byobtaining the oxidation of a predetermined quantity of surplus thiol insuch a way as to obtain in the first case a ratio of the disulfidegroups to the thiol groups greater than 1,5, and in the second case, aratio greater than 2.

Among the oxidizing agents that produce in situ the disulfides startingfrom corresponding thiols, the following can be mentioned: oxidizedwater (hydrogen peroxide), sodium iodate, sodium periodate, sodiumbromate, etc.

In order to make the invention more readily understandable, severalexamples of the two processes according to the invention are describedbelow by way of illustration.

Example 1 To obtain a permanent deformation of hair, a solution composedof the following ingredients is prepared at the time of application:

thioglycerol 5 g dithiodiglycerol 15,85 g ammonia, qsp pH 9,5

urea 4 g mono-oleate of polyoxyethylenatcd sorbitan 0,4 g water qsp lOOg Each strand of hair is saturated with this solution and set on rollersof 8 to 10 mm. in diameter. When all the hair has been set on rollers,it is again saturated with the same solution. The head is covered with acap, and a period of 20 to 25 minutes is allowed to elapse.

The hair, still on rollers, is then abundantly and carefully rinsed withlukewarm water; the rollers are taken off and the hair is rinsed again.I

The curl thus obtained is well set and soft; it lends itself to pleasantstyling, and the condition of the hair remains good. After 6 weeks, noloss of curl is apparent. Example 2 In order to obtain a permanentdeformation of hair, a solution containing the following ingredients isprepared at the time of application:

thioglycerol 4 g dithiodiglycerol 17 g mono-ethanolamine, qsp pH 9,2urea 4 g mono-oleate of polyoxyethylenated sorbitan 0,4 g or Tween(d=l,06l,l0, viscosity 230-430 centistokes) water qsp Example 3 Toobtain the straightening of naturally frizzy hair,

the following composition is prepared, in a creamy texture, by mixingthe following ingredients:

Wax 7 g (made of a mixture of 30 percent cetylic alcohol and 70 percentstearylic alcohol, this mixture being oxyethylenated by 30 moles ofethylene oxide per mole of alcohol in the mixture) thioglycerol 2 gbromide of trimethyl cetyl ammonium 0,2 g dithiodiglycerol 6,35 gammonia, qsp pH 9,5 perfume 0,3 g water qsp 100 g The cream thusobtained is applied to the hair to be straightened strand by strand.Care should be taken to mix the cream well into each strand, so that itbe well saturated.

The hair is then combed backward for a few moments, so that theconsistency of the cream will keep the hair well saturated while theaction of the composition is allowed to take place.

After about 15 minutes the hair is carefully rinsed so as to eliminatethe cream while keeping the hair as much as possible in a stretchedposition.

The hair which, before the treatment, was tightly curled and frizzy hasbecome smooth without being stiff.

The hair, however, now has a soft wide wave, while its texture hasremained in excellent condition.

The ends have remained in good condition, and no cracking has been notedin the area of the roots. Example 4 To obtain a permanent deformation ofthe hair, a solution composed of the following ingredients is preparedat the time of the application:

thioglycolic acid 3,5 g dithiodiglycerol 16 g ammonia, qsp pH 9,5

urea 4 g mono-oleate of polyoxyethylenated sorbitan 0,4 g water qsp 100g The hair is saturated with the aforementioned solution, and it is seton rollers of about 8 to 10 mm. in diameter.

To complete saturation of the hair, the rolled strands of hair aresaturated again with the same solution, and the hair is covered with acap.

After waiting for about minutes, the rollers are removed, the hair isrinsed very rapidly with water and sponged with a towel.

The result is a very beautiful curl, soft to the touch. The curl isdurable and no change is'observed in the wave even after a lapse of 4 to5 weeks.

Example 5 To obtain a permanent deformation of the hair, a solutioncomposed of the following ingredients is prepared at the time ofapplication:

thioglycolic acid 2 g dithiodiglycerol 23,2 g mono-ethanolamine, qsp pH9,0

diethylene triamino pentacetic acid 0,] g ethanol 5 g water qsp 100 gAfter shampooing and sponging the hair, strand by strand the hair issaturated with the aformentioned solution and set on rollers of about 8to 10 mm. in diameter.

After the rollers are all in, the rolled strands of hair are saturatedonce more with the same solution, and the head is covered with a cap. Awaiting period of 20 to 25 minutes is allowed to take place.

The hair is then thoroughly rinsed with tepid water, and the rollers areremoved. The hair is rinsed one more time.

The curl thus obtained is well set and soft; the styling is pleasant andthe condition of the hair has remained good.

After a lapse of 6 weeks, no loss of curl is noted. Example 6 To obtaina permanent deformation in ordinary hair, a solution composed of thefollowing ingredients is prepared at the time of application:

dimercapto-adipic acid 4 g dithiodiglycerol 12 g ammonia, qsp pH l0 ureal0 g water qsp l00 g This solution is applied as indicated in Example 5,with the difference that the time of application is reduced to about 15to 20 minutes. A good permanent wave of the hair is thus obtained.

Example 7 To obtain a permanent deformation in bleached hair, a solutioncontaining the following ingredients is pre pared at the time ofapplication:

dimercapto-adipic acid 3 g dithiodiglycerol 15 g mono-ethanolamine, qsppH 9,0

urea 4 g monoleate of polyoxyethylenated sorbitan 0,4 g water qsp 100 gBy following the same operational mode as that described in Example 2,it is obtained after the last rinsing shiny hair and pleasant to thetouch.

The curl thus obtained is deep, has beautiful styling and does not alterfor several weeks.

Example 8 To obtain, according to the invention, a straightening ofnaturally frizzy hair, a creamy composition is prepared from thefollowing ingredients:

thioglycolic acid 3 g dithiodiglycolic acid 18 g mono-ethanolamine, qsppH 9,0 wax 7 g (made of a mixture of 30 percent cetylic alcohol andpercent of stearylic alcohol; this mixture is oxyethylenated by means of33 moles of ethylene oxide per mole of alcohol in the mixture) bromideof trimethylcetylammonium 0,2 g perfume 0,3 g water g This cream isapplied in the same operational mode described in Example 3. Excellentresults are likewise obtained, and the hair is left with a very widewave. Example 9 To obtain, according to the invention, a permanentdeformation of the hair, a solution is prepared at the moment of theapplication containing the following ingredients:

dimercapto-1,4 butanediol-2,3 2,5 g dithiodiglycerol 5 g ammonia, qsp pH9,7

urea 10 g water qsp I00 g This solution is applied in the sameoperational mode as that described in Example 1. Excellent results arelikewise obtained, and the hair presents a well set and soft curl evenafter a lapse of 6 weeks.

Example 10 To obtain a permanent deformation of the hair, at the momentof application a solution is prepared containing the followingingredients:

thiolactic acid 3 g dithiodiglycerol 15,2 g ammonia, qsp pH 9,4

urea 10 g water qsp 100 g After shampooing and sponging the hair, theoperator saturates each strand of hair with the prementioned solutionand sets it on roller of 8 to 10 mm. in diameter.

When all the rollers are on, the hair is saturated once more with thesame solution. The head is covered with a cap, and a period of 20 to 25minutes is allowed to elapse.

The hair is then rinsed carefully and thoroughly with lukewarm water;the curlers are removed, and the hair is rinsed again.

The curl thus obtained is well set and soft; it presents pleasantstyling, and the condition of the hair remains good.

After a lapse of to 6 weeks, no loss of curl is noted. Example 11 Toobtain a permanent deformation of the hair, a solution is prepared atthe time of application. The following ingredients are included:

thiolactic acid 5 g dithiodiglycerol 30 g mono-ethanolamine, qsp pH 8,7

diethylene triamino pentacetic acid 0,1 g ethanol 5 g water qsp 100 gthioglycolic acid 5 g dithiodiglycolic acid 25 g ammonia, qsp pH 9,3

urea g water qsp 100 g This solution is applied as indicated in Example4, and a good permanent wave is obtained.

Example 13 To obtain, according to the invention, the straightening ofnaturally frizzy hair, a cream compounded as follows is prepared:

thioglycerol dithiodiglycerol l monoethanolamine qsp pH 9.5 wax composedof a mixture of:

30 percent cetylic alcohol and 70 percent stearylic alcohol, thismixture being oxyethylenated by 33 moles of ethylene oxide per mole ofalcohol in the mixture ammonium cetyl trimethyl bromide perfume waterqsp n-nop SUNQ (BROOM This cream, applied in the same conditions as inExample 3, produces an excellent straightening of frizzy hair. The hairnow appears with a slight wave. Example 14 To obtain a permanent settingaccording to the invention, a solution containing the followingingredients must be prepared:

thioglycerol 5 g dithiodiglycerol 16,85 g ammonia, qsp pH 9,5

urea 10 g water qsp I00 g The hair is then saturated and set on rollersof about 15 to 20 mm. in diameter. The solution is left to react during15 to 20 minutes. The hair, still on rollers, is then rinsed and driedby heat externally produced. After the rollers are removed and the hairis combed out, a very satisfactory coiffure is obtained.

Example 15 To obtain a permanent setting according to the invention, acomposition is first prepared by mixing the following ingredients:

thioglycerol 5 g dithiodiglycerol 40 g monoethanolamine qsp pH 8,5

diethylene triamino pentacetic acid 0,] g

ethanol 5 g water qsp g The hair is saturated with the solution thusobtained,

then set on rollers of about 15 to 20 mm. in diameter. After a settingperiod of about 15 to 20 minutes, the hair is carefully rinsed and thendried by means of heat externally produced.

After the rollers have been removed and the hair has been combed out, anexcellent coiffure is obtained. Example 16 To obtain a permanentsetting, a composition is first prepared by mixing the followingingredients:

thioglycolic acid 2 g dithiodiglycolic acid 20 g ammonia, qsp pH 10 urea10 g water qsp 100 g thioglycolic acid 5 g dithiodiglycerol 35 gmonoethanolamine, qsp-pH 8,5 triamino diethylene pentacetic acid 0,1 gethanol 5 g water qsp 100 g The hair is saturated, strand by strand, andis set on rollers of about 15 to 20 mm. in diameter. Setting on therollers takes place immediately after each strand is saturated with thesolution.

After a period of setting of about 15 to 20 minutes, the hair is rinsedvery carefully. The next step is drying, heat being produced externally.

After the hair is thoroughly dried, the rollers are removed, and thehair is combed out. Excellent resiliency of the strands is obtained. Thestyling effect produced at this time lasts, and the hair is pleasant tobehold and to touch.

Example 18 To obtain a permanent setting according to the invention, acomposition is prepared by mixing the following ingredients:

dimercaptoadipic acid 4 g dithiodiglycerol 12 g ammonia, qsp pH urea 10g water qsp 100 g By proceeding as indicated in the preceding Example, apermanent setting of very good appearance is obtained.

Example 19 To obtain a permanent setting according to the invention, acomposition is prepared by mixing the following ingredientsidimercapto-l,4 butanediol-2,3 2,5 g dithiodiglycerol g ammonia, qsp pH9,7

urea 10 g water qsp 100 g By operating as in Example 17, an excellentpermanent setting is obtained whereby the hair appears with a very goodwave.

Example 20 To obtain a permanent setting according to the invention, acomposition is prepared by mixing the following ingredients:

thiolactic acid 2 g dithiodiglycerol 20 g ammonia, qsp pH 10 triaminodiethylene pentacetic acid 0,] g ethanol 5 g water qsp 100 g CompositionA thioglycolic acid 28,25 g monoethanolamine qsp pH 9,6 perfume 0,4 gwater qsp 100 g Composition B aqueous solution of hydrogen peroxide 17,2volumes.

At the time of use compositions A and B are mixed volume to volume.After one minute the internal temperature was about 70C and after 10minutes about 43C.

After the 10 minutes laps, analysis of the mixture give the followingfigures:

thioglycolic acid dithiodiglycolic acid By using this composition asdescribed in example 10 an excellent curl is obtained which does notloose even after 6 weeks. Example 22 To obtain a permanent deformationof hair according to the invention the two following compositions areprepared: Composition A thioglycolic acid 20 g ammonia, qsp toneutralize monoethanolamine, qsp pH 9,5

perfume 0,3 g water qsp 8 Composition B aqueous solution of hydrogenperoxide 10 volumes. At the time of use composition A and B are mixedvolume to volume. From time 0 to 10 minutes the internal temperaturefigures are:

time 0 21C 30 sec 41C 10 mn 32C After the 10 minutes laps, analysis ofthe mixture give the following figures:

thioglycolic acid dithiodiglycolic acid pH 9,4

By using this composition according to Example 1 a perfect permanentwave is obtained.

What is claimed is: v

1. A process which produces a permanent deformation of the hair wherein:

the hair is subjected to mechanical deformation and treated with asufiicient amount of self-neutralizing composition containing in aqueousor hydroalcoholic solution, a mixture of: thiol with a concentration of2 to 5 percent, said thiol being selected from the group consisting of:thioglycerol, thioglycolic acid, dimercapto-adipic acid, dimercapto-l ,4buta'nediol-2,3, and thiolactic acid; and disulfide, said disulfidebeing dithiodiglycerol, the numerical ratio of the disulfide groups tothe thiol groups being greater than 1,5 and said composition having a pHcontained between 8,5 and l0;

the composition is left to set for a period of time be- 13 14 I thecomposition is left to react during a period of tion having a pH between8,5 and 10;

time contained between S and 30 minutes; the composition is left toreact during a period of mechanical deformation is relieved; and timecontained between and 30 minutes;

the hair i rin dthe hair, still on rollers, is rinsed; and

A Process accordmg to clalm 2, Where"! the hall 5 the hair is dried byheat externally provided. is saturated with the composition before it issubjected process which produces permanent setting of to mechanicaldeformation. the hair wherein;

Pmcess f q to clam wherein the the hair is rolled on curlers of about 15to 20 mm. in chamfial fieformatlon produced by rollers of 8 to 10diameter, and treated with a sufficient amount of m d'ameter' m aself-neutralizing composition containing in aque- 5. A process accordingto claim 2, wherein mechani- (ms or hydroalcoholic Solution a mixture ofcal deformation is produced by combing and the com- 2 5 f I d osition isapplied in the form of a cream. P i 0 10 an p dithlodiglycolic acid witha numerical ratio of the 6. A process which produces permanent settingof disulfide groups to the thiol groups being greater the hair wherein:

the hair is set on rollers of 15 to mm. in diameter,

and treated with a sufiicient amount of a selfneutralizing compositioncontaining, in aqueous or hydroalcoholic solution, a mixture of: a thiolhaving a concentration between 2 and 5 per- 20 cent, said thiol beingselected from the group consisting of: thioglycerol, thioglycolic acid,dimercapthan 2, and the said composition having a pH between 8,5 and10.; the composition is left to react during a period of time containedbetween 5 and minutes; the hair, still on rollers, is rinsed; and thehair is dried by heat externally provided. 8. A process according toclaim 7, wherein:

to-adipic acid, dimercapto-l,4 butanediol-2,3, a d the hair is rinsedafter the standing period of 5 to 30 thiolactic acid, and minutes; and

a disulfide, said disulfide being dithiodiglycerol, the 5 the hair issaturated by an aqueous, or hydroalcoholic numerical ratio of thedisulfide groups to the thiol solution containing a resin.

groups being greater than 1,5, and said composic UNITED STATES PATENTOFFICE CERTIFICATE -O-F CORRECTION Patent No. 3,768,490 'Dated October30 1973 v h GREGOIRE KALOPISSIS ET AL It is certified that error appearsin the aboveddentified patent andthat said Letters Patent are herebycorrected as shown below:

On the cover sheet, insert [30] Foreign Appli'cation, Priority DataFrance 983,968 August 3, 1964 France 995,597 November 19,. 1964 France.5,818 February- 16, 1965 France 5,819 February 16, 1965 Signed andsealed this 6th day of August 1974.

(SEAL) Attes t MCCOY M. GIBSON, JR. c. MARSHALL DANN Atte sting OfficerCommissioner of Patents FORM po'wso "$59) US'COMM-DC 00376-P69 9 .5,GOVERNMENT PR'NT'NG OFFICE Z IQ, O366-334.

2. A process which produces a permanent deformation of the hair wherein:the hair is subjected to mechanical deformation and treated with asufficient amount of a self-neutralizing composition containing inaqueous or hydroalcoholic solution, a mixture of: 2 to 5 percent ofthioglycolic acid, and dithiodiglycolic acid, the numerical ratio of thedisulfide groups to the thiol groups being greater than 2 and saidcomposition having a pH of 8,5 and 10; the composition is left to reactduring a period of time contained between 5 and 30 minutes; mechanicaldeformation is relieved; and the hair is rinsed.
 3. A process accordingto claim 2, wherein the hair is saturated with the composition before itis subjected to mechanical deformation.
 4. A process according to claim2, wherein the mechanical deformation is produced by rollers of 8 to 10mm. in diameter.
 5. A process according to claim 2, wherein mechanicaldeformation is produced by combing and the composition is applied in theform of a cream.
 6. A process which produces permanent setting of thehair wherein: the hair is set on rollers of 15 to 20 mm. in diameter,and treated with a sufficient amount of a self-neutralizing compositioncontaining, in aqueous or hydroalcoholic solution, a mixture of: a thiolhaving a concentration between 2 and 5 percent, said thiol beingselected from the group consisting of: thioglycerol, thioglycolic acid,dimercapto-adipic acid, dimercapto-1,4 butanediol-2,3, and thiolacticacid, and a disulfide, said disulfide being dithiodiglycerol, thenumerical ratio of the disulfide groups to the thiol groups beinggreater than 1,5, and said composition having a pH between 8,5 and 10;the composition is left to react during a period of time containedbetween 5 and 30 minutes; the hair, still on rollers, is rinsed; and thehair is dried by heat externally provided.
 7. A process which producespermanent setting of the hair wherein: the hair is rolled on curlers ofabout 15 to 20 mm. in diameter, and treated with a sufficient amount ofa self-neutralizing composition containing in aqueous or hydroalcoholicsolution a mixture of: 2 to 5 percent of thioglycolic acid, anddithiodiglycolic acid with a numerical ratio of the disulfide groups tothe thiol groups being greater than 2, and the said composition having apH between 8,5 anD 10.; the composition is left to react during a periodof time contained between 5 and 30 minutes; the hair, still on rollers,is rinsed; and the hair is dried by heat externally provided.
 8. Aprocess according to claim 7, wherein: the hair is rinsed after thestanding period of 5 to 30 minutes; and the hair is saturated by anaqueous, or hydroalcoholic solution containing a resin.